JP6481058B2 - Flame retardant urethane resin composition - Google Patents

Description

  The present invention relates to a flame retardant urethane resin composition.

Concrete reinforced with reinforcing bars or the like is used for apartment houses such as condominiums, detached houses, various facilities of schools, and outer walls of commercial buildings.
Concrete has the advantage of maintaining strength over a long period of time as a structural material.
On the other hand, in hot weather such as summer, there is a disadvantage that heat is accumulated in concrete due to outside air or direct sunlight, and the inside of the building is heated by the accumulated heat.
In addition, the concrete is cooled not only in summer but also in cold periods such as winter. As a result, the interior of the building is cooled.
In this way, the outside temperature may affect the inside of the building for a long time through the concrete. In order to reduce this effect, heat insulation is usually applied to concrete.
For example, in the case of concrete reinforced by reinforcing bars used in apartment houses such as apartment buildings, a hard polyurethane foam is sprayed on the concrete surface to form a heat insulating layer.
However, if the hard polyurethane foam is merely sprayed as the heat insulating layer, the hard polyurethane foam may burn if a fire or the like occurs inside the building. In order to prevent the hard polyurethane foam from burning, a fire-resistant material called white cement, which is mainly composed of volcanic ash, cement or the like, is sprayed on the surface of the hard polyurethane foam.
By using the white cement, it is possible to prevent the rigid polyurethane foam from burning.
However, after forming a heat insulation layer by spraying hard polyurethane foam on the surface of the concrete, a two-stage spraying operation is required when forming a fireproof layer by spraying white cement on the surface of the hard polyurethane foam. Because of this, there was a problem that it took time for construction.
In addition, after the rigid polyurethane foam is sprayed, the next construction process cannot proceed until the rigid polyurethane foam sufficiently reacts, and after the white cement is sprayed on the surface of the rigid polyurethane foam, the white polyurethane foam There was also a problem that the next construction process could not proceed until the cement curing reaction was completed, and it took time for construction.

On the other hand, a first prior art for imparting a self-extinguishing function to a polyurethane foam in preparation for a case where a polyurethane foam formed by molding a urethane resin composition burns has also been studied.
This first prior art describes that a polyurethane foam containing aluminosilicates exhibits self-extinguishing properties (Patent Document 1).
However, in the case of polyurethane foam containing aluminosilicates having self-extinguishing properties, increasing the proportion of the content of aluminosilicates rapidly impairs the fluidity of the urethane resin composition containing the aluminosilicates, making it difficult to handle. There was a problem.

Further, the followings are also disclosed as prior art related to polyurethane foam.
Specifically, a second prior art for a polyol composition for rigid polyurethane foam containing a polyol compound, a water-soluble organic solvent, a catalyst, a flame retardant, a foaming agent, and a polyisocyanate compound has also been studied (Patent Document 2).
It is described in this prior art that a rigid polyurethane foam formed by mixing and foaming these components is excellent in flame retardancy.

  A third prior art for a non-combustible panel in which non-combustible boards are installed on both sides of a polyurethane foam molded article formed by reacting isocyanate and polyol as main raw materials and reacting the main raw materials in the presence of a catalyst and a foaming agent. Technology has also been studied (Patent Document 3).

  Also, a fourth prior art for a polyol composition for polyurethane foam containing 100 parts by weight of a polyol compound, 10 to 30 parts by weight of a phosphate ester flame retardant, a foaming agent, a foam stabilizer and a catalyst has been studied (Patent Document). 4).

  In addition, a fifth prior art for a flame retardant composition in which polymer particles and a solid flame retardant are dispersed in a liquid organic polyisocyanate has been studied (Patent Document 5).

  In addition, a sixth prior art regarding a flame retardant composition in which an alkoxylate quaternary ammonium borate ester salt is combined with an inorganic flame retardant and / or an organic flame retardant has been studied (Patent Document 6).

  In addition, the seventh prior art on a flame-retardant rigid polyurethane foam obtained by reacting and curing a polyhydroxyl compound, a polyisocyanate, a urethanization catalyst, a flame retardant, a foam stabilizer, and a foaming agent has been studied (Patent Literature). 7).

  Further, an eighth prior art for a catalyst composition for producing a rigid polyurethane foam and / or an isocyanurate-modified rigid polyurethane foam comprising a quaternary ammonium salt and a heterocyclic tertiary amine compound is also being studied ( Patent Document 8).

(A) at least one organic polyisocyanate;
(B) (b1) a polyol compound having a functionality of 2-8 and a hydroxyl number of 20-800, 0 to 99% by weight, and (b2) a functionality of 1-8 and a hydroxyl number of 15-200 of at least 1 A polyol composition containing 100 to 1% by mass of a polyol compound of the type, wherein the mass% is based on the total amount of the polyol component (b), and (b2) is a solid substance dispersed in the carrier polyol (b2ii) A copolymer polyol composition comprising (b2i), wherein (b2) comprises a dispersion of at least 2% and not more than 60% solids (b2i), wherein at least 2% of said carrier polyol (b2ii) comprises a tertiary amine A polyol composition which is a polyol (b2iii) based on
(C) optionally in the presence of a blowing agent;
(D) Optionally, the ninth prior art on a method for producing a polyurethane product by reacting a mixture with an additive or adjuvant known in the production of polyurethane products is also being studied (Patent Document 9). ).

  In addition, a tenth prior art in which a urethane resin contains a trivalent phosphorus compound and / or a pentavalent organic phosphate as a flame retardant has been studied (Patent Document 10).

And (A) at least one organic phosphorus compound having a selected group consisting of the group HP = O, the group PH, and the group P-OH;
(B) Formula (I) [R ′ (Y) m ′] m (X—O—R ″) n [wherein R ′ is an organic group. Y is hydroxy, carboxylic acid, carboxylate, acid 15 A functional group selected from an anhydride, amine, —SH, —SO ₃ H, —CONH ₂ , —NHCOOR, phosphite and phosphinate groups. X is a hydrocarbylene group. R ″ is hydrogen or carbon number. 1 to 8 hydrocarbyl groups. R is an alkyl or aryl group having 1 to 12 carbon atoms. m ′, m and n are each independently one or more numbers. The 11th prior art about the phosphorus containing compound obtained by making it react with the at least 1 sort (s) of compound which has] is also examined (patent document 11).

(1) organic polyisocyanate,
(2) at least one compound having a plurality of isocyanate-reactive groups,
(3) Internal mold release system comprising (a) carboxylic acid and (b) a compound selected from the group consisting of fatty acid polyesters, fatty acid esters, and fatty acid amides, and a reaction system comprising the above (1) to (3) A twelfth prior art is also being studied (Patent Document 12).

However, all the above prior arts disclose nothing about solving the problem that the polyurethane foam is likely to change its shape when it is affected by heat such as a fire.
When the polyurethane foam is deformed by heat such as a fire, a gap is generated between the place where the polyurethane foam was installed and the deformed polyurethane foam. There arises a problem that smoke or the like generated by a fire or the like diffuses through the gap.

JP-A-9-169863 JP 2010-053267 A JP 2004-050495 A JP 2002-338651 A Japanese Patent Laid-Open No. 3-152159 Japanese Patent Laid-Open No. 61-261331 Japanese Patent Laid-Open No. 2001-200027 JP 2010-7079 A JP 2005-500417 A JP 2009-187885 A JP 2008-501063 A Japanese National Patent Publication No. 11-512125

  When examined in more detail, among the above prior arts, the first to fifth, seventh to eighth, tenth and twelfth prior arts do not disclose the use of red phosphorus. For this reason, it is unclear from these prior arts whether or not the polyurethane foam maintains a certain shape when heated.

The sixth prior art also includes N, N, N-tris (polyoxyethylene) -N-tallow aliphatic quaternary ammonium propylene glycol / borate salt, tris (2,3-dibromopropyl) phosphate. (TDBP), aromatic polyester polyol, beef tallow primary amine ethylene oxide 5 mol adduct (manufactured by Lion Akzo, Esomine T / 15), silicone surfactant, urethane catalyst (Dabco TMR, manufactured by Air Products), trimerization catalyst It is disclosed that a rigid polyurethane foam can be obtained by adding crude MDI of organic isocyanate to a raw material consisting of T-45 (manufactured by M & T Chemical) and Freon 11 (fluorinated hydrocarbon) (Patent Document) 6 Example 1).
It is also disclosed that red phosphorus can be used as a flame retardant.
However, the problem to be solved by the sixth prior art is to prevent the deterioration of the characteristics of the organic material. How to obtain a polyurethane foam that maintains a certain shape when heated is the sixth. It is unclear from the description of the prior art.

The ninth prior art discloses the use of an alkali metal alkoxide as a polyisocyanate trimerization catalyst that forms polyisocyanurate in the reaction of a polyol compound and a polyisocyanate compound (Patent Document 9). Paragraph [0049]).
It is also disclosed that red phosphorus is used as a flame retardant in addition to a halogen-substituted phosphate (paragraph [0052] of Patent Document 9).
However, it is unclear from the ninth prior art whether a rigid polyurethane foam that does not use an alkali metal alkoxide disclosed in the ninth prior art maintains a certain shape when heated.

The eleventh prior art discloses that red phosphorus can be used as a flame retardant.
Furthermore, the flame resistant polyurethane disclosed in the eleventh prior art is obtained by reacting a phosphorus-containing polyol obtained by reacting the component (A) and the component (B) described above with a polyisocyanate. (Patent Document 11, paragraphs [0158], [0161] and [0166]).
However, the eleventh prior art does not specifically disclose a trimerization catalyst. It is unclear from the eleventh prior art whether any trimerization catalyst can be used to obtain a foam that maintains a certain shape when heated.

  An object of the present invention is to provide a flame retardant urethane resin composition that is easy to handle, has excellent flame retardancy, and can form a foam that maintains a certain shape when heated.

  As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer and an additive are included, and the additive contains red phosphorus as an essential component. It has been found that the flame retardant urethane resin composition is suitable for the purpose of the present invention, and the present invention has been completed.

That is, the present invention
[1] including a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer, and an additive,
The trimerization catalyst is at least one selected from the group consisting of nitrogen-containing aromatic compounds, carboxylic acid alkali metal salts, tertiary ammonium salts and quaternary ammonium salts;
The additive comprises red phosphorus as an essential component, and in addition to red phosphorus, a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide It provides a flame retardant urethane resin composition characterized by combining at least one selected from the above.

One of the present invention is
[2] The additive is in the range of 4.5 to 70 parts by weight based on 100 parts by weight of the urethane resin composed of the polyisocyanate compound and the polyol compound.
The red phosphorus is in the range of 3 to 18 parts by weight based on 100 parts by weight of the urethane resin,
The additive excluding the red phosphorus provides the flame-retardant urethane resin composition according to the above [1], which is in the range of 1.5 to 52 parts by weight based on 100 parts by weight of the urethane resin. .

One of the present invention is
[3] The flame retardant urethane resin composition contains a catalyst,
The said catalyst contains the said trimerization catalyst in the range of 0.6-10 weight part on the basis of 100 weight part of urethane resins which consist of the said polyisocyanate compound and the said polyol compound, The said [1] or [2]. A flame retardant urethane resin composition is provided.

One of the present invention is
[4] The foaming agent according to any one of [1] to [3], wherein the foaming agent is in a range of 0.1 to 30 parts by weight based on 100 parts by weight of a urethane resin composed of the polyisocyanate compound and the polyol compound. The flame-retardant urethane resin composition described is provided.

One of the present invention is
[5] The flame retardant according to any one of the above [1] to [4], wherein the boric acid-containing flame retardant is at least one selected from the group consisting of boron oxide, boric acid and a metal salt of borate. A urethane resin composition is provided.

One of the present invention is
[6] The flame-retardant urethane resin composition according to any one of [1] to [5], wherein an isocyanate index of a urethane resin composed of the polyisocyanate compound and the polyol compound is in a range of 120 to 1000. It is to provide.

The present invention also provides
[7] A foam obtained by molding the flame retardant urethane resin composition according to any one of [1] to [6] is provided.

The present invention also provides
[8] A flame-retardant covering structure obtained by coating a flame retardant urethane resin composition according to any one of [1] to [6] on a structure.

The present invention also provides
[9] A method for producing a flame-retardant urethane resin composition, comprising mixing a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer, and an additive,
The trimerization catalyst is at least one selected from the group consisting of nitrogen-containing aromatic compounds, carboxylic acid alkali metal salts, tertiary ammonium salts and quaternary ammonium salts;
The additive comprises red phosphorus as an essential component, and in addition to red phosphorus, a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide The present invention provides a method for producing a flame retardant urethane resin composition comprising a combination of at least one selected from the above.

  According to the present invention, it is possible to provide a flame retardant urethane resin composition that is easy to handle, has excellent flame retardancy, and gives a foam that maintains a certain shape when heated.

The flame retardant urethane resin composition according to the present invention will be described.
First, the urethane resin used in the flame retardant urethane resin composition will be described.
The urethane resin comprises a polyisocyanate compound as a main agent and a polyol compound as a curing agent.
Examples of the polyisocyanate compound that is the main component of the urethane resin include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.
Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.
The said polyisocyanate compound can use 1 type, or 2 or more types.
The main component of the urethane resin is preferably diphenylmethane diisocyanate for reasons such as ease of use and availability.

  Examples of the polyol compound that is a curing agent for the urethane resin include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polymer polyol, and polyether polyol.

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.
The polycarbonate polyol can be obtained, for example, by dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like. A polyol etc. are mentioned.

Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolak, and cresol novolak.
Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol, and the like.
Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.
Examples of the polyester polyol include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, and a polymer obtained by ring-opening polymerization of a lactone such as ε-caprolactone and α-methyl-ε-caprolactone. And a condensate of hydroxycarboxylic acid and the above polyhydric alcohol.

Specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid.
Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. It is done.
Specific examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

  Examples of the polymer polyol include a polymer obtained by graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate on the aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, and the like. , Polybutadiene polyols, modified polyols of polyhydric alcohols, or hydrogenated products thereof.

Examples of the modified polyol of the polyhydric alcohol include those modified by reacting a raw material polyhydric alcohol with an alkylene oxide.
Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane,
Pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., tetra- to octavalent alcohols such as sucrose, glucose, mannose, fructose, methyl glucoside and derivatives thereof,
Phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, anthrol, 1,4,5 Phenol polybutadiene polyols such as 1,8-tetrahydroxyanthracene and 1-hydroxypyrene,
Castor oil polyol,
Examples include (co) polymers of hydroxyalkyl (meth) acrylates and polyfunctional (eg, 2 to 100 functional group) polyols such as polyvinyl alcohol, and condensates (novolaks) of phenol and formaldehyde.

The method for modifying the polyhydric alcohol is not particularly limited, but a method of adding alkylene oxide (hereinafter abbreviated as AO) is preferably used.
Examples of the AO include AO having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propyloxide, 1,2 -Butylene oxide, 1, 4- butylene oxide, etc. are mentioned.
Among these, PO, EO, and 1,2-butylene oxide are preferable from the viewpoint of properties and reactivity, and PO and EO are more preferable.
When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

Examples of the polyether polyol include ring-opening polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens. And the resulting polymer.
Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol,
Triols such as glycerin and trimethylolpropane,
Examples include amines such as ethylenediamine and butylenediamine.

The polyol used in the present invention is preferably a polyester polyol or a polyether polyol because the effect of reducing the total calorific value upon combustion is great.
Among them, it is more preferable to use a polyester polyol having a molecular weight of 200 to 800, and it is more preferable to use a polyester polyol having a molecular weight of 300 to 500.

The isocyanate index is a percentage of the equivalent ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol compound. When the value exceeds 100, the isocyanate group is in excess of the hydroxyl group. .
The range of the isocyanate index of the urethane resin used in the present invention is preferably in the range of 120 to 1000, more preferably in the range of 200 to 800, and even more preferably in the range of 300 to 600.

  The flame retardant urethane resin composition according to the present invention includes a catalyst, a foam stabilizer and a foaming agent.

  Examples of the catalyst include triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethylaminoethyl. -Nitrogen atom-containing catalysts such as ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N'-dimethylaminoethylpiperazine, imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group Etc.

The addition amount of the catalyst used in the flame retardant urethane resin composition according to the present invention is preferably in the range of 0.6 to 10 parts by weight with respect to 100 parts by weight of the urethane resin, and 0.6 weights. More preferably, the range is from 8 parts to 8 parts, more preferably from 0.6 parts to 6 parts by weight, and most preferably from 0.6 parts to 3.0 parts by weight. .
When the amount is 0.6 parts by weight or more, there is no problem that the formation of urethane bonds is hindered. When the amount is 10 parts by weight or less, an appropriate foaming rate can be maintained and the handling is easy.

  The catalyst used in the present invention includes a trimerization catalyst that causes the isocyanate group contained in the polyisocyanate compound, which is the main component of the polyurethane resin, to react and trimerize to promote the formation of an isocyanurate ring.

In order to promote the formation of an isocyanurate ring, for example, as a catalyst, tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro A nitrogen-containing aromatic compound such as -S-triazine;
Carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate, potassium octylate,
Tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt and triphenylammonium salt, and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt and tetraphenylammonium salt can be used.

The addition amount of the trimerization catalyst used in the flame retardant urethane resin composition according to the present invention is preferably in the range of 0.6 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range of 8 parts by weight to 8 parts by weight, still more preferably in the range of 0.6 to 6 parts by weight, and in the range of 0.6 to 3.0 parts by weight. Most preferred.
In the case of 0.6 parts by weight or more, there is no problem that the trimerization of isocyanate is inhibited, and in the case of 10 parts by weight or less, an appropriate foaming speed can be maintained and handling is easy.

Moreover, the foaming agent used for the flame-retardant urethane resin composition according to the present invention promotes foaming of the urethane resin.
Specific examples of the blowing agent include, for example, water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and other low boiling point hydrocarbons, dichloroethane, propyl chloride, isopropyl chloride. , Chlorinated aliphatic hydrocarbon compounds such as butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride,
Fluorine compounds such as trichloromonofluoromethane and trichlorotrifluoroethane,
Hydrofluorocarbons such as CHF ₃ , CH ₂ F ₂ and CH ₃ F;
Dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), HFC-245fa (1,1 , 1,3,3-pentafluoropropane), hydrochlorofluorocarbon compounds such as HFC-365mfc (1,1,1,3,3-pentafluorobutane),
Examples include organic physical foaming agents such as ether compounds such as diisopropyl ether or mixtures of these compounds, and inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas.

The range of the foaming agent used in the flame retardant urethane resin composition according to the present invention is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the urethane resin.
The foaming agent is more preferably in the range of 0.1 to 18 parts by weight, still more preferably in the range of 0.5 to 18 parts by weight with respect to 100 parts by weight of the urethane resin. Most preferably, it is in the range of 10 to 10 parts by weight.
When the water range is 0.1 parts by weight or more, foaming is promoted, and the density of the resulting molded product can be reduced. When the water content is 30 parts by weight or less, the foam does not break, Can be prevented from being formed.

The flame retardant urethane resin composition according to the present invention contains a foam stabilizer.
Examples of the foam stabilizer include surfactants such as polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ether, silicone foam stabilizers such as organopolysiloxane, and the like.
The amount of the foam stabilizer used for the urethane resin cured by the chemical reaction is appropriately set according to the urethane resin cured by the chemical reaction to be used. For example, for example, 100 parts by weight of the urethane resin On the other hand, the range of 0.1 to 10 parts by weight is preferable.

  The catalyst, the foaming agent, and the foam stabilizer may be used alone or in combination of two or more.

Next, the additive used for this invention is demonstrated.
The flame retardant urethane resin composition according to the present invention includes an additive.
The additive comprises red phosphorus as an essential component, and in addition to red phosphorus, a group consisting of phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, and metal hydroxide A combination of at least one selected from the above.

  There is no limitation in red phosphorus used for this invention, A commercial item can be selected suitably and can be used.

Moreover, it is preferable that the addition amount of red phosphorus used for the fireproof urethane resin composition according to the present invention is in the range of 3.0 to 18 parts by weight with respect to 100 parts by weight of the urethane resin.
When the range of the red phosphorus is 3.0 parts by weight or more, the self-extinguishing property of the flame retardant urethane resin composition according to the present invention is maintained, and when it is 18 parts by weight or less, the flame retardant according to the present invention is maintained. Foaming of the conductive urethane resin composition is not inhibited.

  Further, the phosphate ester used in the present invention is not particularly limited, but it is preferable to use a monophosphate ester, a condensed phosphate ester, or the like.

  The monophosphate ester is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate. , Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid Phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid Examples include diethyl, resilsinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (β-chloropropyl) phosphate, and the like.

The condensed phosphate ester is not particularly limited, and examples thereof include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (trade name PX- manufactured by Daihachi Chemical Industry Co., Ltd.). 200), hydroquinone poly (2,6-xylyl) phosphate and condensed phosphates such as condensates thereof.
Examples of commercially available condensed phosphate esters include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), aromatic condensed phosphate ester (trade name CR747), and resorcinol. Examples thereof include polyphenyl phosphate (manufactured by ADEKA, trade name ADK STAB PFR), bisphenol A polycresyl phosphate (trade names FP-600, FP-700), and the like.

  Among these, it is preferable to use a monophosphate ester because it is highly effective in reducing the viscosity in the composition before curing and reducing the initial calorific value, and using tris (β-chloropropyl) phosphate. Is more preferable.

  The said phosphate ester can use 1 type, or 2 or more types.

Moreover, it is preferable that the addition amount of the phosphate ester used for this invention is the range of 1.5 weight part-52 weight part with respect to 100 weight part of said urethane resins, and 1.5 weight part-20 weight part. Is more preferably in the range of 2.0 to 15 parts by weight, and most preferably in the range of 2.0 to 10 parts by weight.
When the range of the phosphoric acid ester is 1.5 parts by weight or more, the compact made of the flame-retardant urethane resin composition according to the present invention can be prevented from cracking the dense residue formed by the heat of fire, 52 When the amount is not more than parts by weight, foaming of the flame retardant urethane resin composition according to the present invention is not inhibited.

The phosphate-containing flame retardant used in the present invention contains phosphoric acid.
The phosphoric acid used for the phosphate-containing flame retardant is not particularly limited, and examples thereof include various phosphoric acids such as monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.

Examples of the phosphate-containing flame retardant include salts of the various phosphoric acids and at least one metal or compound selected from metals of Group IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. Can be mentioned.
Examples of the metals in groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.
Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like.
Examples of the aromatic amine include pyridine, triazine, melamine, and ammonium.
The phosphate-containing flame retardant may be subjected to a known water resistance improving treatment such as silane coupling agent treatment or coating with a melamine resin, and a known foaming aid such as melamine or pentaerythritol may be added. May be.

  Specific examples of the phosphate-containing flame retardant include monophosphate, pyrophosphate, polyphosphate, and the like.

Although not particularly limited as the monophosphate, for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate,
Sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, sodium hypophosphite,
Potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite,
Lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium hypophosphite,
Barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, barium hypophosphite,
Magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium hypophosphite,
Calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite,
Examples thereof include zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite.

  The polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate.

  Among these, since the self-extinguishing property of the phosphate-containing flame retardant is improved, it is preferable to use a monophosphate, and it is more preferable to use ammonium dihydrogen phosphate.

  The said phosphate containing flame retardant can use 1 type, or 2 or more types.

The addition amount of the phosphate-containing flame retardant used in the present invention is preferably in the range of 1.5 parts by weight to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 parts by weight to 20 parts by weight. More preferably, it is in the range of parts by weight, more preferably in the range of 2.0 parts by weight to 15 parts by weight, and most preferably in the range of 2.0 parts by weight to 10 parts by weight.
When the range of the phosphate-containing flame retardant is 1.5 parts by weight or more, the self-extinguishing property of the flame-retardant urethane resin composition according to the present invention is maintained, and when the range is 52 parts by weight or less, the present invention. Foaming of the flame retardant urethane resin composition according to is not inhibited.

The bromine-containing flame retardant used in the present invention is not particularly limited as long as it is a compound containing bromine in the molecular structure, and examples thereof include aromatic brominated compounds.
Specific examples of the aromatic brominated compound include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (penta Monomeric organic bromine compounds such as bromophenoxy) ethane, ethylene-bis (tetrabromophthalimide), tetrabromobisphenol A,
A polycarbonate oligomer produced from brominated bisphenol A as a raw material, a brominated polycarbonate such as a copolymer of the polycarbonate oligomer and bisphenol A,
Brominated epoxy compounds such as diepoxy compounds produced by reaction of brominated bisphenol A with epichlorohydrin, monoepoxy compounds obtained by reaction of brominated phenols with epichlorohydrin,
Poly (brominated benzyl acrylate),
Brominated polyphenylene ether,
A condensate of brominated bisphenol A, cyanuric chloride and brominated phenol,
Brominated polystyrene such as brominated (polystyrene), poly (brominated styrene), cross-linked brominated polystyrene,
Halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly (-methylstyrene).
From the viewpoint of controlling the calorific value at the initial stage of combustion, brominated polystyrene, hexabromobenzene and the like are preferable, and hexabromobenzene is more preferable.

  One or two or more of the bromine-containing flame retardants can be used.

The amount of bromine-containing flame retardant used in the present invention is preferably in the range of 1.5 parts by weight to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 parts by weight to 20 parts by weight. Is more preferably in the range of 2.0 to 15 parts by weight, and most preferably in the range of 2.0 to 10 parts by weight.
When the range of the bromine-containing flame retardant is 0.1 part by weight or more, the self-extinguishing property of the flame retardant urethane resin composition according to the present invention is maintained, and when it is 52 parts by weight or less, the present invention is concerned. Foaming of the flame retardant urethane resin composition is not inhibited.

Examples of the boron-containing flame retardant used in the present invention include borax, boron oxide, boric acid, and borate.
Examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.
Examples of the borate include alkali metals, alkaline earth metals, elements of Group 4, Group 12, and Group 13 of the periodic table, and ammonium borate.
Specifically, alkali metal borate such as lithium borate, sodium borate, potassium borate, cesium borate, alkaline earth metal borate such as magnesium borate, calcium borate, barium borate, boron Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.

  The boron-containing flame retardant used in the present invention is preferably a borate, and more preferably zinc borate.

  One or more boron-containing flame retardants can be used.

The amount of the boron-containing flame retardant used in the present invention is preferably in the range of 1.5 to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 to 20 parts by weight. The range is more preferable, the range of 2.0 parts by weight to 15 parts by weight is still more preferable, and the range of 2.0 parts by weight to 10 parts by weight is most preferable.
When the range of the boron-containing flame retardant is 1.5 parts by weight or more, the self-extinguishing property of the flame retardant urethane resin composition according to the present invention is maintained, and when it is 52 parts by weight or less, the present invention is concerned. Foaming of the flame retardant urethane resin composition is not inhibited.

Examples of the antimony-containing flame retardant used in the present invention include antimony oxide, antimonate, pyroantimonate and the like.
Examples of the antimony oxide include antimony trioxide and antimony pentoxide.
Examples of the antimonate include sodium antimonate and potassium antimonate.
Examples of the pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.

  The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

  The said antimony containing flame retardant can use 1 type, or 2 or more types.

The addition amount of the antimony-containing flame retardant used in the present invention is preferably in the range of 1.5 parts by weight to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 parts by weight to 20 parts by weight. Is more preferably in the range of 2.0 to 15 parts by weight, and most preferably in the range of 2.0 to 10 parts by weight.
When the range of the antimony-containing flame retardant is 1.5 parts by weight or more, the self-extinguishing property of the flame retardant urethane resin composition according to the present invention is maintained, and when it is 52 parts by weight or less, the present invention is concerned. Foaming of the flame retardant urethane resin composition is not inhibited.

  Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide. , Vanadium hydroxide, tin hydroxide and the like.

  The said metal hydroxide can use 1 type, or 2 or more types.

The addition amount of the metal hydroxide used in the present invention is preferably in the range of 1.5 to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 to 20 parts by weight. Is more preferably in the range of 2.0 to 15 parts by weight, and most preferably in the range of 2.0 to 10 parts by weight.
When the range of the metal hydroxide is 1.5 parts by weight or more, the self-extinguishing property of the flame retardant urethane resin composition according to the present invention is maintained, and when it is 52 parts by weight or less, the present invention is concerned. Foaming of the flame retardant urethane resin composition is not inhibited.

Moreover, the flame retardant urethane resin composition according to the present invention can be used in combination with an inorganic filler.
The inorganic filler is not particularly limited. For example, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, Magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salt of calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, ceviolite, imogolite, seri Site, glass fiber, glass beads, silica balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, dititanate Con lead, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powder, slag fibers, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, and the like.

  The said inorganic filler can use 1 type, or 2 or more types.

  Furthermore, the flame retardant urethane resin composition according to the present invention is a range that does not impair the object of the present invention, as necessary, such as phenol-based, amine-based, sulfur-based antioxidants, heat stabilizers, metal damage. An additive such as an inhibitor, an antistatic agent, a stabilizer, a crosslinking agent, a lubricant, a softener, a pigment, and a tackifier resin, and a tackifier such as a polybutene and a petroleum resin can be included.

  The additive used in the present invention contains red phosphorus as an essential component, and in addition to red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, and metal hydroxide A combination of at least one selected from the group consisting of things.

Examples of preferable combinations of additives used in the present invention include any of the following (a) to (n).
(A) Red phosphorus and phosphate ester (b) Red phosphorus and phosphate containing flame retardant (c) Red phosphorus and bromine containing flame retardant (d) Red phosphorus and boron containing flame retardant (e) Red phosphorus and antimony containing flame retardant Flame retardant (f) Red phosphorus and metal hydroxide (g) Red phosphorus, phosphate ester and phosphate containing flame retardant (h) Red phosphorus, phosphate ester and bromine containing flame retardant (i) Red phosphorus, phosphate ester And boron-containing flame retardant (j) red phosphorus, phosphate-containing flame retardant and bromine-containing flame retardant (k) red phosphorus, phosphate-containing flame retardant and boron-containing flame retardant (l) red phosphorus, bromine-containing flame retardant and Boron-containing flame retardant (m) red phosphorus, phosphate ester, phosphate-containing flame retardant and bromine-containing flame retardant (n) red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant and boron-containing flame retardant Flame retardant

The additive amount used in the present invention is preferably in the range of 4.5 parts by weight to 70 parts by weight with respect to 100 parts by weight of the urethane resin, and the total amount of additives other than the urethane resin is in the range of 4.5 parts by weight, More preferably, it is in the range of 4.5 to 40 parts by weight, still more preferably in the range of 4.5 to 30 parts by weight, and in the range of 4.5 to 20 parts by weight. Is most preferred.
When the range of the additive is 4.5 parts by weight or more, the molded body made of the flame retardant urethane resin composition according to the present invention can prevent the dense residue formed by the heat of fire from cracking, and 70 weight In the case of less than the part, foaming of the flame retardant urethane resin composition according to the present invention is not inhibited.

Since the flame retardant urethane resin composition according to the present invention reacts and cures, its viscosity changes with time.
Therefore, before using the flame retardant urethane resin composition according to the present invention, the flame retardant urethane resin composition is divided into two or more, and the flame retardant urethane resin composition reacts and cures. Prevent it. And when using the flame retardant urethane resin composition according to the present invention, the flame retardant urethane resin composition according to the present invention is integrated into one by dividing the flame retardant urethane resin composition divided into two or more. A resin composition is obtained.
When the flame-retardant urethane resin composition is divided into two or more, each component of the flame-retardant urethane resin composition divided into two or more does not start to cure, and the flame-retardant urethane resin composition What is necessary is just to divide each component so that hardening reaction may start after mixing each component of these.

Next, the manufacturing method of the said flame-retardant urethane resin composition is demonstrated.
Although there is no limitation in particular in the manufacturing method of the said flame-retardant urethane resin composition, For example, the method of mixing each component of the said flame-retardant urethane resin composition, the said flame-retardant urethane resin composition is suspended in the organic solvent Or a method of preparing a slurry by dispersing it in a solvent, preparing a slurry by dispersing in a solvent, and the reaction curable resin component contained in the flame retardant urethane resin composition. When a component that is solid at a temperature of ° C. is contained, the flame retardant urethane resin composition can be obtained by a method such as melting the flame retardant urethane resin composition under heating.

  The flame retardant urethane resin composition is a known component of the flame retardant urethane resin composition, such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a laika machine, and a planetary stirrer. It can obtain by kneading | mixing using the apparatus of.

Alternatively, the main component of urethane resin and the curing agent may be separately kneaded together with a filler or the like and kneaded with a static mixer, a dynamic mixer or the like immediately before injection.
Further, the components of the flame retardant urethane resin composition excluding the catalyst and the catalyst may be kneaded in the same manner immediately before injection.

  The flame-retardant urethane resin composition according to the present invention can be obtained by the method described above.

Next, the curing method of the flame retardant urethane resin composition according to the present invention will be described.
When the respective components of the flame retardant urethane resin composition are mixed, the reaction starts, the viscosity increases with the passage of time, and the fluidity is lost.
For example, the molded body made of the flame retardant urethane resin composition can be obtained as a foam by injecting the flame retardant urethane resin composition into a container such as a mold or a frame material and curing it.
When obtaining the molded object which consists of the said flame-retardant urethane resin composition, heat can be applied or a pressure can be applied.
The molded body made of the flame retardant urethane resin composition is preferably in the range of 0.030 to 0.130 in specific gravity because of easy handling, and more preferably in the range of 0.040 to 0.100. , 0.040 to 0.080 is more preferable, and 0.050 to 0.060 is most preferable.

Next, application examples of the flame retardant urethane resin composition according to the present invention will be described.
By blowing the flame retardant urethane resin composition onto a structure such as a building, furniture, automobile, train, ship, etc., a foam layer made of the flame retardant urethane resin composition is formed on the surface of the structure. be able to.
For example, the flame retardant urethane resin composition is divided into a polyisocyanate compound and other components, mixed while spraying both, and sprayed onto the surface of the structure,
Examples thereof include a method of spraying the surface of the structure after mixing the polyisocyanate compound and the other components.
By the above method, a foam layer can be formed on the surface of the structure.

Next, a fire resistance test performed on a molded body made of the flame retardant urethane resin composition will be described.
A molded body made of the flame retardant urethane resin composition is cut into a length of 10 cm, a width of 10 cm, and a thickness of 5 cm to prepare a sample for a corn calorimeter test.
Using the sample for corn calorimeter test, the total calorific value by the corn calorimeter test when heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes can be measured according to the test method of ISO-5660. .

  Hereinafter, the present invention will be described in detail by way of examples. In addition, this invention is not limited at all by the following examples.

  According to the formulation shown in Table 1, the flame retardant urethane resin composition according to Example 1 was prepared by being divided into three components (A) to (C). In addition, the detail of each component shown to Tables 1-10 is as follows.

(A) component: polyol compound (a) polyol compound A-1: polyol 1
p-phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RFK-505, hydroxyl value = 250 mgKOH / g)
A-2: Polyol 2
o-Phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RDK-142, hydroxyl value: 400 mgKOH / g)
A-3: Polyol 3
o-Phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RDK-121, hydroxyl value: 260 mgKOH / g)
A-4: Polyol 4
p-phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RLK-035, hydroxyl value: 150 mgKOH / g)
A-5: polyol 5
Polyether polyol (Mitsui Chemicals, product name: Actol T-400, hydroxyl value: 399 mgKOH / g)
A-6: Polyol 6
Polyether polyol (Mitsui Chemicals, product name: Actol T-700, hydroxyl value: 250 mgKOH / g)
A-7: Polyol 7
Polyether polyol (Mitsui Chemicals, product name: Actol GR84T, hydroxyl value: 454 mgKOH / g)
A-8: Polyol 8
Polyether polyol (Mitsui Chemicals, product name: Actcol SOR400, hydroxyl value: 397 mgKOH / g)
(B) Foam stabilizer Foam stabilizer containing polyalkylene glycol (manufactured by Toray Dow Corning, product name: SH-193)
(C) Catalyst [Trimerization catalyst]
B-1: Potassium 2-ethylhexanoate (manufactured by Tokyo Chemical Industry Co., Ltd., product code: P0048)
-B-2: Trimerization catalyst (product name: TOYOCAT-TR20 manufactured by Tosoh Corporation)
B-3: Trimerization catalyst (manufactured by Toei Chemical Co., product name: 15% potassium hexaate)
[Urethane catalyst]
・ Pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT-DT)
(D) Foaming agent, water, HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Central Glass Co., Ltd.)
HFC-245fa (1,1,1,3,3-pentafluoropropane, manufactured by Nippon Solvay)
Mixing ratio: HFC-365mfc: HFC-245fa = 7: 3 (weight ratio; hereinafter referred to as “HFC”)
・ Pentane

Component (B): isocyanate compound (hereinafter referred to as “polyisocyanate”)
MDI (manufactured by Nippon Urethane Industry Co., Ltd., product name: Millionate MR-200) Viscosity: 167 mPa · s

(C) Component: Additive C-1: Red phosphorus (Rin Chemical Industry Co., Ltd., product name: Nova Excel 140)
C-2: ammonium dihydrogen phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)
C-3: Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP, hereinafter referred to as “TMCPP”)
C-4: Hexabromobenzene (manac product, product name: HBB-b, hereinafter referred to as “HBB”)
-C-5: Zinc borate (Hayakawa Shoji, product name: Firebrake ZB)
C-6: antimony trioxide (Nippon Seiko Co., Ltd., product name: Patox C)
C-7: Aluminum hydroxide (Almorix, product name: B-325)
C-8: Diammonium hydrogen phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)
C-9: primary aluminum phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)
C-10: sodium monophosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)
C-11: ammonium polyphosphate (manufactured by Clariant Japan, product name: AP422)
C-12: halogen-containing condensed phosphate ester (manufactured by Daihachi Chemical Co., Ltd., product name: DAIGUARD-540)
C-13: Non-halogen condensed phosphate ester (product name: CR-733S, manufactured by Daihachi Chemical Co., Ltd.)
C-14: ethylene-bis (tetrabromophthalimide) (manufactured by Albemarle, product name: SAYTEXBT-93, hereinafter referred to as “EBTBPI”)
C-15: ethylene-bis (pentabromophenyl) (manufactured by Albemarle, product name: SAYTEX 8010, hereinafter referred to as “EBPBP”)

Next, according to the mixing | blending of following Table 1, (A) component of a polyol compound and (C) component of an additive were weighed in a 1000 mL polypropylene beaker, and it stirred by hand-mixing at 25 degreeC for 1 minute.
The (B) component was added to the kneaded mixture of the (A) component and the (C) component after stirring, and the mixture was stirred for about 10 seconds to prepare a foam.
The obtained flame-retardant urethane resin composition lost fluidity with the passage of time, and a foam of the flame-retardant urethane resin composition was obtained. The foam was evaluated according to the following criteria, and the results are shown in Table 1.

[Measurement of calorific value]
A sample for corn calorimeter test was cut out from the cured product so as to be 10 cm × 10 cm × 5 cm, and the maximum heat generation rate and total heat generation when heated for 20 minutes at a radiant heat intensity of 50 kW / m ² in accordance with ISO-5660 Was measured.
The results are shown in Tables 1-10.
This measurement method is a test method stipulated as corresponding to the standard according to the corn calorimeter method at the Building Comprehensive Testing Laboratory, which is a public institution stipulated in Article 108-2 of the Building Standards Act Enforcement Ordinance. It conforms to the test method of ISO-5660.

[Measurement of expansion]
When the test of ISO-5660 was carried out, it was described in Tables 1 to 10 as x when the molded body after expansion was in contact with the igniter and ◯ when it was not in contact.

[Measurement of deformation (cracking)]
When the test of ISO-5660 was carried out, the deformation reaching the back surface of the test sample was observed as x, and when the deformation reaching the back surface was not observed, the results were shown in Tables 1 to 10. did.

[Measurement of shrinkage]
When the test of ISO-5660 was carried out, the test sample was evaluated as x when a deformation of 1 cm or more in the lateral direction and 5 mm or more was observed in the thickness direction, and ○ when no deformation was observed. -10.

[Comprehensive evaluation]
All the measurement results of the measurement of heat quantity, the measurement of expansion, the measurement of deformation (crack cracking), and the measurement of shrinkage are shown as “OK” for “◯”, and “NG” for the others.

Compared to the case of Example 1, the amount of red phosphorus used was changed from 3.0 parts by weight of Example 1 to 6.0 parts by weight, and the amount of ammonium dihydrogen phosphate was changed to 9 of Example 1. The experiment was performed in the same manner as in Example 1 except that the amount was changed from 0.0 parts by weight to 3.0 parts by weight.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 1 to 4.6 parts by weight, and the amount of red phosphorus used was 3.0 of Example 1. Except for the change from 1 part by weight to 12.0 parts by weight and the amount of ammonium dihydrogen phosphate used was changed from 9.0 parts by weight to 6.0 parts by weight in Example 1, the same as in Example 1. The experiment was conducted in the same manner.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 1 to 4.8 parts by weight, and the amount of red phosphorus used was 3.0 of Example 1. Except for the change from 1 part by weight to 18.0 parts by weight and the amount of ammonium dihydrogen phosphate used was changed from 9.0 parts by weight to 6.0 parts by weight in Example 1, it was completely the same as in Example 1. The experiment was conducted in the same manner.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 1 to 4.7 parts by weight, and the amount of red phosphorus used was 3.0 of Example 1. Except for the change from 10.0 parts by weight to 10.0 parts by weight and the amount of ammonium dihydrogen phosphate used was changed from 9.0 parts by weight to 10.0 parts by weight in Example 1, the same as in Example 1. The experiment was conducted in the same manner.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 1 to 3.7 parts by weight, and the amount of red phosphorus used was 3.0 of Example 1. The experiment was performed in exactly the same manner as in Example 1 except that the weight was changed to 6.0 parts by weight and that 7.0 parts by weight of TMCPP was used instead of ammonium dihydrogen phosphate.
The results are shown in Table 1.

Compared to the case of Example 6, the amount of foaming agent HFC used was changed from 3.7 parts by weight of Example 6 to 4.7 parts by weight, and the amount of red phosphorus used was 6.0 of Example 6. The experiment was performed in exactly the same manner as in Example 1 except that the amount was changed from 1 part by weight to 13.3 parts by weight and the amount of TMCPP used was changed from 7.0 parts by weight to 6.7 parts by weight. went.
The results are shown in Table 1.

Compared to the case of Example 7, the amount of red phosphorus used was changed from 13.3 parts by weight of Example 7 to 10.0 parts by weight, and the amount of TMCPP used was 6.7 parts by weight of Example 7. The experiment was performed in the same manner as in Example 1 except that the amount was changed from 10.0 to 10.0 parts by weight.
The results are shown in Table 1.

Compared to the case of Example 8, the amount of red phosphorus used was changed from 10.0 parts by weight of Example 8 to 4.0 parts by weight, and the amount of TMCPP used was 10.0 parts by weight of Example 8. The experiment was performed in the same manner as in Example 1 except that the amount was changed from 1 to 16.0 parts by weight.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 1 to 3.7 parts by weight, and the amount of red phosphorus used was 3.0 of Example 1. The experiment was performed in exactly the same manner as in Example 1, except that the weight was changed from 3.3 parts by weight to 3.3 parts by weight, and 1.7 parts by weight of HBB was used instead of ammonium dihydrogen phosphate.
The results are shown in Table 1.

Compared to the case of Example 10, the amount of foaming agent HFC used was changed from 3.7 parts by weight of Example 10 to 3.8 parts by weight, and the amount of red phosphorus used was 3.3 of Example 10. The experiment was performed in exactly the same manner as in Example 10, except that the weight part was changed to 6.0 parts by weight, and the amount of HBB used was changed from 1.7 parts by weight to 3.0 parts by weight. went.
The results are shown in Table 2.

Compared to the case of Example 10, the amount of foaming agent HFC used was changed from 3.7 parts by weight of Example 10 to 4.5 parts by weight, and the amount of red phosphorus used was 3.3 of Example 10. The experiment was performed in the same manner as in Example 10, except that the weight was changed from 13.3 parts by weight to 13.3 parts by weight, and the amount of HBB used was changed from 1.7 parts by weight in Example 10 to 6.7 parts by weight. went.
The results are shown in Table 2.

Compared to the case of Example 10, the amount of foaming agent HFC used was changed from 3.7 parts by weight of Example 10 to 4.3 parts by weight, and the amount of red phosphorus used was 3.3 of Example 10. The experiment was performed in the same manner as in Example 10, except that the weight part was changed to 10.0 parts by weight, and the amount of HBB used was changed from 1.7 parts by weight to 10.0 parts by weight in Example 10. went.
The results are shown in Table 2.

Compared to the case of Example 10, the amount of foaming agent HFC used was changed from 3.7 parts by weight of Example 10 to 4.1 parts by weight, and the amount of red phosphorus used was 3.3 of Example 10. The experiment was carried out in the same manner as in Example 10, except that the weight part was changed to 4.0 parts by weight, and the amount of HBB used was changed from 1.7 parts by weight to 16.0 parts by weight. went.
The results are shown in Table 2.

Compared to the case of Example 11, the experiment was performed in the same manner as in Example 11 except that 6.0 parts by weight of zinc borate was used instead of HBB.
The results are shown in Table 2.

As compared with the case of Example 11, the experiment was performed in the same manner as in Example 11 except that 3.0 parts by weight of antimony trioxide was used instead of HBB.
The results are shown in Table 2.

Compared to the case of Example 11, the experiment was performed in the same manner as in Example 11 except that 3.0 parts by weight of aluminum hydroxide was used instead of HBB.
The results are shown in Table 2.

Compared to the case of Example 1, the amount of red phosphorus used was changed from 3.0 parts by weight of Example 1 to 3.8 parts by weight, and the amount of ammonium dihydrogen phosphate was changed to 9 of Example 1. The experiment was performed in the same manner as in Example 1 except that the amount was changed from 0.0 parts by weight to 1.9 parts by weight and that 4.4 parts by weight of TMCPP was used.
The results are shown in Table 2.

Compared to the case of Example 18, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 18 to 4.6 parts by weight, and the amount of red phosphorus used was 3.8 of Example 18. The weight was changed from 6.0 parts by weight to 6.0 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 1.9 parts by weight of Example 18 to 3.0 parts by weight, and the amount of TMCPP used was changed to Example 18. The experiment was performed in exactly the same manner as in Example 18 except that the amount was changed from 4.4 parts by weight to 7.0 parts by weight.
The results are shown in Table 2.

Compared to the case of Example 19, the amount of foaming agent HFC used was changed from 4.6 parts by weight of Example 19 to 4.7 parts by weight, and the amount of red phosphorus used was 6.0 of Example 19. The weight was changed from 7.5 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 3.0 parts by weight of Example 19 to 3.8 parts by weight, and the amount of TMCPP was changed to Example 19. The experiment was performed in the same manner as in Example 19 except that the weight was changed from 7.0 parts by weight to 8.8 parts by weight.
The results are shown in Table 2.

Compared to the case of Example 20, the amount of foaming agent HFC used was changed from 4.7 parts by weight of Example 20 to 6.4 parts by weight, and the amount of red phosphorus used was 7.5 of Example 20. The weight was changed from 15.0 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 3.8 parts by weight of Example 20 to 7.5 parts by weight, and the amount of TMCPP used was changed to Example 20. The experiment was performed in exactly the same manner as in Example 20 except that the weight was changed from 8.8 parts by weight to 17.5 parts by weight.
The results are shown in Table 3.

Compared to the case of Example 1, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 1 to 3.5 parts by weight, and the amount of red phosphorus used was 3.0 of Example 1. The weight was changed from 5.0 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 9.0 parts by weight of Example 1 to 2.5 parts by weight, and HBB was used by 2.5 parts by weight. The experiment was performed in exactly the same manner as in Example 1 except that.
The results are shown in Table 3.

Compared to the case of Example 22, the amount of foaming agent HFC used was changed from 3.5 parts by weight of Example 22 to 3.9 parts by weight, and the amount of red phosphorus used was 5.0 of Example 22. The weight was changed from 6.0 parts by weight to 6.0 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 2.5 parts by weight of Example 22 to 3.0 parts by weight, and the amount of HBB used was changed to Example 22. The experiment was performed in the same manner as in Example 22 except that the amount was changed from 2.5 parts by weight to 3.0 parts by weight.
The results are shown in Table 3.

Compared to the case of Example 22, the amount of foaming agent HFC used was changed from 3.5 parts by weight of Example 22 to 4.5 parts by weight, and the amount of red phosphorus used was 5.0 of Example 22. The weight was changed from 10.0 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 2.5 parts by weight of Example 22 to 5.0 parts by weight, and the amount of HBB used was changed to Example 22. The experiment was performed in the same manner as in Example 22 except that the amount was changed from 2.5 parts by weight to 5.0 parts by weight.
The results are shown in Table 3.

Compared to the case of Example 22, the amount of foaming agent HFC used was changed from 3.5 parts by weight of Example 22 to 5.5 parts by weight, and the amount of red phosphorus used was 5.0 of Example 22. The amount changed from 2 parts by weight to 20.0 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 2.5 parts by weight of Example 22 to 10.0 parts by weight, and the amount of HBB used was changed to Example 22. The experiment was performed in exactly the same manner as in Example 22 except that the weight was changed from 2.5 parts by weight to 10.0 parts by weight.
The results are shown in Table 3.

Compared to the case of Example 22, the amount of foaming agent HFC used was changed from 3.5 parts by weight of Example 22 to 3.9 parts by weight, and the amount of red phosphorus used was 5.0 of Example 22. It was changed from 4.8 parts by weight to 3.8 parts by weight, 4.4 parts by weight of TMCPP was used instead of ammonium dihydrogen phosphate, and the amount of HBB used was changed from 2.5 parts by weight of Example 22 to 1.9 parts by weight. The experiment was performed in the same manner as in Example 22 except that the weight part was changed.
The results are shown in Table 3.

Compared to the case of Example 26, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 26 to 4.4 parts by weight, and the amount of red phosphorus used was 3.8 of Example 26. The weight was changed from 6.0 parts by weight, the amount of TMCPP used was changed from 4.4 to 7.0 parts by weight of Example 26, and the amount of HBB used was 1.9 of Example 26. The experiment was performed in the same manner as in Example 26 except that the weight was changed to 3.0 parts by weight.
The results are shown in Table 3.

Compared to the case of Example 26, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 26 to 4.6 parts by weight, and the amount of red phosphorus used was 3.8 of Example 26. The weight was changed from 7.5 parts by weight, the amount of TMCPP used was changed from 4.4 parts by weight of Example 26 to 8.8 parts by weight, and the amount of HBB used was 1.9 of Example 26. The experiment was performed in the same manner as in Example 26 except that the weight was changed to 3.8 parts by weight.
The results are shown in Table 3.

Compared to the case of Example 26, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 26 to 6.1 parts by weight, and the amount of red phosphorus used was 3.8 of Example 26. The weight was changed from 15.0 parts by weight, the amount of TMCPP used was changed from 4.4 parts by weight of Example 26 to 17.5 parts by weight, and the amount of HBB used was 1.9 of Example 26. The experiment was performed in the same manner as in Example 26 except that the weight was changed to 7.5 parts by weight.
The results are shown in Table 3.

Compared to the case of Example 22, the amount of foaming agent HFC used was changed from 3.5 parts by weight of Example 22 to 4.3 parts by weight, and the amount of red phosphorus used was 5.0 of Example 22. The weight was changed from 6.0 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 2.5 parts by weight in Example 22 to 3.0 parts by weight, and zinc borate was used instead of HBB. The experiment was performed in the same manner as in Example 22 except that 6.0 parts by weight were used.
The results are shown in Table 3.

Compared to the case of Example 22, the amount of foaming agent HFC used was changed from 3.5 parts by weight of Example 22 to 4.4 parts by weight, and the amount of red phosphorus used was 5.0 of Example 22. Except for changing from 6.0 parts by weight to 6.0 parts by weight, using 7.0 parts by weight of TMCPP instead of ammonium dihydrogen phosphate, and using 6.0 parts by weight of zinc borate instead of HBB. The experiment was performed in exactly the same manner as in Example 22.
The results are shown in Table 4.

Compared to the case of Example 31, the amount of foaming agent HFC used was changed from 4.4 parts by weight of Example 31 to 4.2 parts by weight, and 3.0 parts by weight of HBB was used instead of TMCPP. The experiment was performed in the same manner as in Example 31 except that.
The results are shown in Table 4.

Compared to the case of Example 18, the amount of red phosphorus used was changed from 3.8 parts by weight of Example 18 to 3.2 parts by weight, and the amount of ammonium dihydrogen phosphate used was 1 of Example 18. 1.9 parts by weight was changed to 1.6 parts by weight, the amount of TMCPP used was changed from 4.4 parts by weight in Example 18 to 3.6 parts by weight, and HBB was used by 1.6 parts by weight. The experiment was performed in the same manner as in Example 18 except for the above.
The results are shown in Table 4.

Compared to the case of Example 33, the amount of blowing agent HFC used was changed from 3.9 parts by weight of Example 33 to 4.7 parts by weight, and the amount of red phosphorus used was 3.2 of Example 33. The weight was changed from 6.0 parts by weight to 6.0 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 1.6 parts by weight of Example 33 to 3.0 parts by weight, and the amount of TMCPP used was changed to Example 33. The amount of HBB was changed from 7.0 parts by weight to 7.0 parts by weight, and the amount of HBB used was changed from 1.6 parts by weight of Example 33 to 3.0 parts by weight. The experiment was conducted in the same manner.
The results are shown in Table 4.

Compared to the case of Example 33, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 33 to 6.0 parts by weight, and the amount of red phosphorus used was 3.2 of Example 33. The weight was changed from 9.5 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 1.6 parts by weight of Example 33 to 4.7 parts by weight, and the amount of TMCPP used was changed to Example 33. Except for changing from 3.6 parts by weight to 11.1 parts by weight, and changing the amount of HBB used from 1.6 parts by weight of Example 33 to 4.7 parts by weight, it is completely the same as in Example 33. The experiment was conducted in the same manner.
The results are shown in Table 4.

Compared to the case of Example 33, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 33 to 6.4 parts by weight, and the amount of red phosphorus used was 3.2 of Example 33. The amount changed from 1 part by weight to 12.6 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 1.6 parts by weight of Example 33 to 6.3 parts by weight, and the amount of TMCPP used was changed to Example 33. Except that the amount of HBB was changed from 3.6 parts by weight to 14.8 parts by weight, and the amount of HBB used was changed from 1.6 parts by weight of Example 33 to 6.3 parts by weight. The experiment was conducted in the same manner.
The results are shown in Table 4.

Compared to the case of Example 33, the amount of foaming agent HFC used was changed from 3.9 parts by weight of Example 33 to 7.9 parts by weight, and the amount of red phosphorus used was 3.2 of Example 33. The weight was changed from 15.8 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 1.6 parts by weight of Example 33 to 7.9 parts by weight, and the amount of TMCPP used was changed to Example 33. Except that the amount of HBB was changed from 3.6 parts by weight to 18.4 parts by weight and the amount of HBB used was changed from 1.6 parts by weight of Example 33 to 7.9 parts by weight. The experiment was conducted in the same manner.
The results are shown in Table 4.

Compared to the case of Example 33, the amount of blowing agent HFC used was changed from 3.9 parts by weight of Example 33 to 4.7 parts by weight, and the amount of red phosphorus used was 3.2 of Example 33. The weight was changed from 6.0 parts by weight to 6.0 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 1.6 parts by weight of Example 33 to 3.0 parts by weight, and the amount of TMCPP used was changed to Example 33. The amount of HBB used was changed from 7.0 parts by weight to 7.0 parts by weight, the amount of HBB used was changed from 1.6 parts by weight of Example 33 to 3.0 parts by weight, and zinc borate was changed to 6.0 parts by weight. The experiment was performed in the same manner as in Example 33 except that a part of the sample was used.
The results are shown in Table 4.

Compared to the case of Example 34, the amount of polyol compound A-1 used was changed from 21.8 parts by weight of Example 34 to 35.8 parts by weight, and the amount of polyisocyanate used was 78 of Example 34. Except for the change from 2 parts by weight to 64.2 parts by weight, and the amount of foaming agent HFC used was changed from 4.7 parts by weight in Example 34 to 4.6 parts by weight, it was completely the same as in Example 34. The experiment was conducted in the same manner.
The results are shown in Table 4.

Compared to the case of Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight of Example 39 to 27.1 parts by weight, and the amount of polyisocyanate used was 64 of Example 39. The experiment was performed in the same manner as in Example 39 except that the amount was changed from 2 parts by weight to 72.9 parts by weight.
The results are shown in Table 4.

Compared to Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight to 18.2 parts by weight of Example 39, and the amount of polyisocyanate used was 64 of Example 39. The experiment was performed in the same manner as in Example 39 except that the amount was changed from 2 parts by weight to 81.8 parts by weight.
The results are shown in Table 5.

Compared to the case of Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight of Example 39 to 15.7 parts by weight, and the amount of polyisocyanate used was 64 of Example 39. The experiment was performed in the same manner as in Example 39 except that the amount was changed from 2 parts by weight to 84.3 parts by weight.
The results are shown in Table 5.

Compared to the case of Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight of Example 39 to 13.7 parts by weight, and the amount of polyisocyanate used was 64 of Example 39. The experiment was performed in the same manner as in Example 39 except that the amount was changed from 2 parts by weight to 86.3 parts by weight.
The results are shown in Table 5.

Compared to the case of Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight of Example 39 to 12.2 parts by weight, and the amount of polyisocyanate used was 64 of Example 39. The experiment was performed in the same manner as in Example 39 except that the amount was changed from 2 parts by weight to 87.8 parts by weight.
The results are shown in Table 5.

Compared to the case of Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight of Example 39 to 11.0 parts by weight, and the amount of polyisocyanate used was 64 of Example 39. The experiment was performed in the same manner as in Example 39 except that the weight was changed from 2 parts by weight to 89.0 parts by weight.
The results are shown in Table 5.

Compared to the case of Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight of Example 39 to 10.0 parts by weight, and the amount of polyisocyanate used was 64 of Example 39. The experiment was performed in the same manner as in Example 39 except that the amount was changed from 2 parts by weight to 90.0 parts by weight.
The results are shown in Table 5.

Compared to the case of Example 39, 16.6 parts by weight of polyol compound A-2 was used instead of polyol compound A-1, and the amount of polyisocyanate used was changed from 64.2 parts by weight of Example 39 to 83 parts. The experiment was performed in the same manner as in Example 39 except that the amount was changed to 4 parts by weight.
The results are shown in Table 5.

Compared to the case of Example 39, 21.4 parts by weight of polyol compound A-3 was used instead of polyol compound A-1, and the amount of polyisocyanate used was changed from 64.2 parts by weight of Example 39 to 78 parts by weight. The experiment was performed in the same manner as in Example 39 except that the amount was changed to 6 parts by weight.
The results are shown in Table 5.

Compared to the case of Example 39, 27.6 parts by weight of polyol compound A-4 was used instead of polyol compound A-1, and the amount of polyisocyanate used was changed from 64.2 parts by weight of Example 39 to 72 parts by weight. The experiment was performed in the same manner as in Example 39 except that the amount was changed to 4 parts by weight.
The results are shown in Table 5.

Compared to the case of Example 39, 21.8 parts by weight of polyol compound A-5 was used instead of polyol compound A-1, and the amount of polyisocyanate used was changed from 64.2 parts by weight of Example 39 to 78 parts. The experiment was performed in the same manner as in Example 39 except that the amount was changed to 2 parts by weight.
The results are shown in Table 5.

Compared to the case of Example 39, 16.6 parts by weight of polyol compound A-6 was used instead of polyol compound A-1, and the amount of polyisocyanate used was changed from 64.2 parts by weight of Example 39 to 83. The experiment was performed in the same manner as in Example 39 except that the amount was changed to 4 parts by weight.
The results are shown in Table 6.

Compared to the case of Example 39, 15.3 parts by weight of polyol compound A-7 was used instead of polyol compound A-1, and the amount of polyisocyanate used was changed from 64.2 parts by weight of Example 39 to 84 parts by weight. The experiment was performed in the same manner as in Example 39 except that the amount was changed to 7 parts by weight.
The results are shown in Table 6.

Compared to the case of Example 39, 16.7 parts by weight of polyol compound A-8 was used instead of polyol compound A-1, and the amount of polyisocyanate used was changed from 64.2 parts by weight of Example 39 to 83. The experiment was performed in the same manner as in Example 39 except that the amount was changed to 3 parts by weight.
The results are shown in Table 6.

Compared with the case of Example 39, the usage-amount of polyol compound A-1 was changed into 21.8 weight part from 35.8 weight part of Example 39, and the usage-amount of a trimerization catalyst of Example 39 was changed. B-1 was changed from 0.5 part by weight and B-2 to 0.7 part by weight, B-1 was changed to 1.3 part by weight and B-2 was changed to 1.7 part by weight, use of polyisocyanate The experiment was performed in the same manner as in Example 39 except that the amount was changed from 64.2 parts by weight of Example 39 to 78.2 parts by weight.
The results are shown in Table 6.

Compared to the case of Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight of Example 39 to 21.8 parts by weight, to trimerization catalysts B-1 and B-2. Instead, 0.8 part by weight of B-3 was used, and the amount of polyisocyanate was changed from 64.2 parts by weight of Example 39 to 78.2 parts by weight. The experiment was conducted in the same manner.
The results are shown in Table 6.

Compared to the case of Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight to 21.8 parts by weight of Example 39, and the amount of B-1 used as a trimerization catalyst was changed. It changed from 0.5 weight part to 1.0 weight part, B-2 was not used, and the usage-amount of polyisocyanate was changed from 64.2 weight part of Example 39 to 78.2 weight part. Except that, the experiment was performed in the same manner as in Example 39.
The results are shown in Table 6.

Compared to the case of Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight of Example 39 to 29.5 parts by weight. Example 39 except that the amount used was changed from 4.6 parts by weight to 10.0 parts by weight, and the amount of polyisocyanate used was changed from 64.2 parts by weight to 70.5 parts by weight in Example 39. The experiment was performed exactly as in the case.
The results are shown in Table 6.

Compared to Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight of Example 39 to 21.8 parts by weight, and the amount of HFC used was 4.6 parts by weight. The experiment was performed in the same manner as in Example 39 except that the amount was changed to 16.0 parts by weight and the amount of polyisocyanate used was changed from 64.2 parts by weight to 78.2 parts by weight. .
The results are shown in Table 6.

Compared to Example 39, the amount of polyol compound A-1 used was changed from 35.8 parts by weight to 21.8 parts by weight of Example 39, no HFC was used, The experiment was performed in the same manner as in Example 39 except that the amount used was changed from 64.2 parts by weight to 78.2 parts by weight.
The results are shown in Table 6.

Compared with the case of Example 39, the usage-amount of polyol compound A-1 was changed into 34.8 weight part of Example 39 from 25.8 weight part, and the usage-amount of the water of a foaming agent was 0.6. Except for changing from parts by weight to 0.3 parts by weight, not using HFC, and using polyisocyanate from 64.2 parts by weight in Example 39 to 75.2 parts by weight. The experiment was performed in exactly the same way as in 39.
The results are shown in Table 6.

Compared to the case of Example 6, the amount of HFC used was changed from 3.7 parts by weight to 3.5 parts by weight, except that 3.0 parts by weight of diammonium hydrogen phosphate was used instead of TMCPP. The experiment was performed in the same manner as in Example 6.
The results are shown in Table 7.

As compared with the case of Example 61, an experiment was performed in the same manner as in Example 61 except that 3.0 parts by weight of primary aluminum phosphate was used instead of diammonium hydrogen phosphate.
The results are shown in Table 7.

The experiment was performed in the same manner as in Example 61 except that 3.0 parts by weight of primary sodium phosphate was used instead of diammonium hydrogen phosphate as compared with Example 61.
The results are shown in Table 7.

As compared with Example 61, the experiment was performed in exactly the same manner as in Example 61 except that 3.0 parts by weight of ammonium polyphosphate was used instead of diammonium hydrogen phosphate.
The results are shown in Table 7.

Compared to Example 61, the amount of HFC used was changed from 3.5 parts by weight to 4.0 parts by weight, and 7.0 parts by weight of phosphate ester 1 was used instead of diammonium hydrogen phosphate. The experiment was performed in the same manner as in Example 61 except that.
The results are shown in Table 7.

As compared with the case of Example 65, the experiment was performed in exactly the same manner as in Example 65 except that 7.0 parts by weight of the phosphate ester 2 was used instead of the phosphate ester 1.
The results are shown in Table 7.

Compared to the case of Example 61, 3.0 parts by weight of ammonium dihydrogen phosphate and 7.0 parts by weight of TMCPP were used, and 3.0 parts by weight of EBTBPI was used instead of diammonium hydrogen phosphate. The experiment was performed in the same manner as in Example 61.
The results are shown in Table 7.

As compared with the case of Example 67, the experiment was performed in the same manner as in Example 67 except that 3.0 parts by weight of EBTBP was used instead of EBTBPI.
The results are shown in Table 7.

Compared to the case of Example 33, the amount of polyol compound A-1 used was changed from 21.8 parts by weight of Example 33 to 15.8 parts by weight, and the amount of polyisocyanate used was 78 of Example 33. .2 parts by weight to 84.2 parts by weight, the amount of blowing agent HFC used was changed from 3.9 parts by weight of Example 33 to 4.4 parts by weight, and the amount of red phosphorus used was Example 33 was changed from 3.2 parts by weight to 3.8 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 1.6 parts by weight to 1.9 parts by weight, and TMCPP was used. The amount was changed from 3.6 parts by weight in Example 33 to 4.4 parts by weight, and the amount of HBB used was 1.6 in Example 33.
The experiment was performed in the same manner as in Example 33 except that the weight was changed to 1.9 parts by weight.
The results are shown in Table 7.

Compared to the case of Example 33, the amount of polyol compound A-1 used was changed from 21.8 parts by weight of Example 39 to 17.7 parts by weight, and the amount of polyisocyanate used was 78 of Example 33. It was changed from 2 parts by weight to 82.3 parts by weight, the amount of red phosphorus used was changed from 3.2 parts by weight of Example 33 to 3.0 parts by weight, and the amount of ammonium dihydrogen phosphate used was changed. The change from 1.6 parts by weight in Example 33 to 1.5 parts by weight, the use amount of TMCPP from 3.6 parts by weight in Example 33 to 3.5 parts by weight, the use amount of HBB The experiment was performed in the same manner as in Example 33 except that the amount was changed from 1.6 parts by weight in Example 33 to 1.5 parts by weight.
The results are shown in Table 7.

Compared to the case of Example 33, the amount of polyol compound A-1 used was changed from 21.8 parts by weight of Example 39 to 16.8 parts by weight, and the amount of polyisocyanate used was 78 of Example 33. The amount of HFC used was changed from 3.9 parts by weight to 83.2 parts by weight, the amount of HFC used was changed from 3.9 parts by weight to 6.0 parts by weight, and the amount of red phosphorus used was 3.2 wt. Part 9.6 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 1.6 parts by weight in Example 33 to 4.8 parts by weight, and the amount of TMCPP used in Example 33 The amount of HBB used was changed from 1.6 parts by weight of Example 33 to 4.8 parts by changing from 3.6 parts by weight to 11.2 parts by weight.
The experiment was performed in exactly the same manner as in Example 33 except that the weight parts were changed.
The results are shown in Table 8.

Compared to the case of Example 71, the amount of polyol compound A-1 used was changed from 16.8 parts by weight of Example 71 to 30.6 parts by weight, and the amount of polyisocyanate used was 83 of Example 71. The experiment was performed in the same manner as in Example 71 except that the amount was changed from 2 parts by weight to 69.4 parts by weight.
The results are shown in Table 8.

Compared to the case of Example 71, the amount of polyol compound A-1 used was changed from 16.8 parts by weight of Example 71 to 26.4 parts by weight, and the amount of HFC used was changed from 6.0 parts by weight. It was changed to 6.4 parts by weight, the amount of polyisocyanate used was changed from 83.2 parts by weight of Example 71 to 70.6 parts by weight, and the amount of red phosphorus used was 9.6% by weight of Example 71. 13.3 parts by weight, the amount of ammonium dihydrogen phosphate used was changed from 4.8 parts by weight of Example 71 to 6.6 parts by weight, and the amount of TMCPP used in Example 71 Except for changing from 11.2 parts by weight to 15.5 parts by weight, and by changing the amount of HBB used from 4.8 parts by weight of Example 71 to 6.6 parts by weight, it is exactly the same as in Example 33. The experiment was conducted.
The results are shown in Table 8.

The experiment was performed in exactly the same manner as in Example 34 except that the amount of foam stabilizer used was changed from 1.7 parts by weight of Example 34 to 6.8 parts by weight as compared with Example 34. It was.
The results are shown in Table 8.

The experiment was performed in exactly the same manner as in Example 34 except that the amount of foam stabilizer used was changed from 1.7 parts by weight of Example 34 to 10.0 parts by weight as compared with Example 34. It was.
The results are shown in Table 8.

As compared with the case of Example 34, the experiment was performed in the same manner as in the case of Example 34 except that the urethanization catalyst was not used.
The results are shown in Table 8.

[Comparative Example 1]
Compared to the case of Example 1, the amount of polyol compound A-1 used was changed from 21.8 parts by weight of Example 1 to 52.7 parts by weight, the trimerization catalyst was not used, and HFC The amount of polyisocyanate used was changed from 3.9 parts by weight to 6.4 parts by weight, the amount of polyisocyanate used was changed from 78.2 parts by weight to 47.3 parts by weight, and additives were used. The experiment was performed in exactly the same manner as in Example 1 except that it was not performed.
The results are shown in Table 9.

[Comparative Example 2]
Compared to the case of Example 1, the amount of HFC used was changed from 3.9 parts by weight to 3.2 parts by weight and the same as in Example 1 except that the additive was not used. The experiment was conducted.
The results are shown in Table 9.

[Comparative Example 3]
Compared to the case of Comparative Example 2, the amount of HFC used was changed from 3.2 parts by weight to 3.3 parts by weight, and the case of Example 2 except that 3.0 parts by weight of red phosphorus was used. The experiment was conducted in exactly the same way.
The results are shown in Table 9.

[Comparative Example 4]
Compared to the case of Comparative Example 2, the amount of HFC used was changed from 3.2 parts by weight to 3.4 parts by weight, except that red phosphorus was used by 6.0 parts by weight. The experiment was conducted in exactly the same way.
The results are shown in Table 9.

[Comparative Example 5]
Compared to the case of Comparative Example 2, the amount of HFC used was changed from 3.2 parts by weight to 4.0 parts by weight, and the case of Example 2 except that 12.0 parts by weight of red phosphorus was used. The experiment was conducted in exactly the same way.
The results are shown in Table 9.

[Comparative Example 6]
Compared to the case of Comparative Example 2, the amount of HFC used was changed from 3.2 parts by weight to 4.8 parts by weight, and the case of Example 2 except that 24.0 parts by weight of red phosphorus was used. The experiment was conducted in exactly the same way.
The results are shown in Table 9.

[Comparative Example 7]
Compared to the case of Example 34, the amount of polyol compound A-1 used was changed from 21.8 parts by weight to 25.0 parts by weight of Example 34, no blowing agent was used, Example 34 except that the amount used was changed from 4.7 parts by weight to 6.4 parts by weight and the amount of polyisocyanate used was changed from 78.2 parts by weight to 75.0 parts by weight in Example 34. The experiment was performed exactly as in the case.
The results are shown in Table 9.

[Comparative Example 8]
Compared to the case of Example 34, the amount of HFC used was changed from 4.7 parts by weight to 4.4 parts by weight, and the same as in Example 34, except that red phosphorus was not used. The experiment was conducted.
The results are shown in Table 9.

[Comparative Example 9]
Compared with the case of Comparative Example 8, the amount of HFC used was changed from 4.4 parts by weight to 4.5 parts by weight, except that 6.0 parts by weight of zinc borate was used instead of HBB. The experiment was performed in the same manner as in the case of 8.
The results are shown in Table 9.

[Comparative Example 10]
Compared to the case of Comparative Example 8, the amount of HFC used was changed from 4.4 parts by weight to 4.3 parts by weight, except that 6.0 parts by weight of zinc borate was used instead of TMCPP. The experiment was performed in the same manner as in the case of 8.
The results are shown in Table 9.

[Comparative Example 11]
Compared to the case of Comparative Example 9, the experiment was performed in exactly the same manner as in Comparative Example 9, except that 3.0 parts by weight of HBB was used instead of ammonium dihydrogen phosphate.
The results are shown in Table 10.

[Comparative Example 12]
Compared to the case of Example 1, the amount of HFC used was changed from 3.9 parts by weight to 3.7 parts by weight, and the amount of red phosphorus used was changed from 3.0 parts by weight to 2.0 parts by weight. The experiment was performed in exactly the same manner as in Example 1 except that the amount of ammonium dihydrogen phosphate used was changed from 9.0 parts by weight to 1.0 part by weight.
The results are shown in Table 10.

[Comparative Example 13]
Compared to the case of Example 1, the amount of HFC used was changed from 3.9 parts by weight to 5.8 parts by weight, and the amount of red phosphorus used was changed from 3.0 parts by weight to 24.0 parts by weight. The experiment was performed in exactly the same manner as in Example 1 except that the amount of ammonium dihydrogen phosphate used was changed from 9.0 parts by weight to 12.0 parts by weight.
The results are shown in Table 10.

[Comparative Example 14]
Compared to the case of Example 1, the amount of HFC used was changed from 3.9 parts by weight to 4.6 parts by weight, and the amount of red phosphorus used was changed from 3.0 parts by weight to 2.3 parts by weight. The experiment was conducted in the same manner as in Example 1 except that TMCPP was changed to 2.7 parts by weight instead of ammonium dihydrogen phosphate.
The results are shown in Table 10.

[Comparative Example 15]
Compared to the case of Example 1, the amount of HFC used was changed from 3.9 parts by weight to 5.8 parts by weight, and the amount of red phosphorus used was changed from 3.0 parts by weight to 18.5 parts by weight. The experiment was performed in exactly the same manner as in Example 1 except that TMCPP was changed to 21.5 parts by weight instead of ammonium dihydrogen phosphate.
The results are shown in Table 10.

[Comparative Example 16]
Compared to the case of Example 1, the amount of HFC used was changed from 3.9 parts by weight to 5.8 parts by weight, and the amount of red phosphorus used was changed from 3.0 parts by weight to 26.7 parts by weight. The experiment was performed in exactly the same manner as in Example 1 except that HBB was changed to 13.3 parts by weight instead of ammonium dihydrogen phosphate.
The results are shown in Table 10.

[Comparative Example 17]
Compared to Example 34, the amount of HFC used was changed from 4.7 parts by weight to 3.4 parts by weight, and the amount of red phosphorus used was changed from 6.0 parts by weight to 1.6 parts by weight. The amount of ammonium dihydrogen phosphate used was changed from 3.0 parts by weight to 0.8 parts by weight, the amount of TMCPP used was changed from 7.0 parts by weight to 1.8 parts by weight, HBB The experiment was performed in the same manner as in Example 34 except that the amount of was changed from 3.0 parts by weight to 0.8 parts by weight.
The results are shown in Table 10.

[Comparative Example 18]
Compared to the case of Example 34, the amount of polyol compound A-1 used was changed from 21.8 parts by weight of Example 34 to 52.7 parts by weight, and the amount of HFC used was changed from 4.7 parts by weight. The experiment was performed in exactly the same manner as in Example 34, except that the amount was changed to 4.6 parts by weight and the amount of polyisocyanate used was changed from 78.2 parts by weight to 47.3 parts by weight. .
The results are shown in Table 10.

[Comparative Example 19]
Compared to Example 34, 0.5 parts by weight of B-1 and 0.7 parts by weight of B-2 of the trimerization catalyst were 0 parts by weight of B-1 and 0.1 parts by weight of B-2, respectively. The experiment was performed in the same manner as in Example 34 except that the amount was changed to parts by weight and the amount of HFC used was changed from 4.7 parts by weight to 4.6 parts by weight.
The results are shown in Table 10.

[Comparative Example 20]
Compared to Example 34, 0.5 parts by weight of B-1 and 0.7 parts by weight of B-2 of the trimerization catalyst were 0.3 parts by weight of B-1 and 0 parts by weight of B-2, respectively. The experiment was performed in the same manner as in Example 34 except that the amount was changed to parts by weight and the amount of HFC used was changed from 4.7 parts by weight to 4.6 parts by weight.
The results are shown in Table 10.

[Comparative Example 21]
Compared to Example 34, 0.5 parts by weight of B-1 and 0.7 parts by weight of B-2 of the trimerization catalyst were 0.2 parts by weight of B-1 and 0 parts by weight of B-2, respectively. The experiment was performed in the same manner as in Example 34 except that the amount was changed to 3 parts by weight and the amount of HFC used was changed from 4.7 parts by weight to 4.6 parts by weight.
The results are shown in Table 10.

The molded product obtained from the flame-retardant urethane resin composition according to the present invention has a small amount of heat generated when it burns, and the residue after combustion maintains a certain shape, so that it can exhibit excellent fire resistance. .
Since the molded product of the flame-retardant urethane resin composition according to the present invention is excellent in fire resistance, the flame-retardant urethane resin composition of the present invention can be widely applied to buildings and the like.

Claims (6)

A flame retardant urethane resin composition comprising a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer and a flame retardant ,
The flame retardant has red phosphorus as an essential component,
When the foam made of the flame retardant urethane resin composition is heated at a radiant heat intensity of 50 kW / m ^{2 in} accordance with the test method of ISO-5660, the total calorific value after 10 minutes is 7. A flame retardant urethane resin composition characterized by being 8 MJ / m ² or less . When the foam made of the flame retardant urethane resin composition is heated at a radiant heat intensity of 50 kW / m ^{2 in} accordance with the test method of ISO-5660, the total calorific value after 10 minutes is 7. 8 MJ / ^{m 2} or less, the total amount of heat generated during the elapsed 20 minutes is 12.7MJ / ^{m 2} or less, the flame retardant urethane resin composition according to claim 1, wherein the. In addition to the red phosphorus, the flame retardant is at least one selected from the group consisting of phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants and metal hydroxides. claim 1 or flame-retardant urethane resin composition according to 2, characterized in that it contains. Wherein the flame retardant, Ri range der of 4.5 to 70 parts by weight of the polyisocyanate compound and 100 parts by weight of urethane resin consisting of the polyol compound based,
The red phosphorus is in the range of 3 to 18 parts by weight based on 100 parts by weight of the urethane resin,
The flame retardant urethane resin composition in any one of Claims 1-3 whose flame retardant except the said red phosphorus is the range of 1.5-52 weight part on the basis of 100 weight part of said urethane resins . The flame-retardant urethane resin composition according to any one of claims 1 to 4 , wherein an isocyanate index of the urethane resin is in a range of 120 to 1,000. A foam comprising the flame retardant urethane resin composition according to any one of claims 1 to 5.